| Autor: |
Palos, Etienne, Caruso, Alessandro, Paesani, Francesco |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 11/14/2023, Vol. 159 Issue 18, p1-9, 9p |
| Abstrakt: |
Delocalization error constrains the accuracy of density functional theory in describing molecular interactions in ion–water systems. Using Na+ and Cl− in water as model systems, we calculate the effects of delocalization error in the SCAN functional for describing ion–water and water–water interactions in hydrated ions, and demonstrate that density-corrected SCAN (DC-SCAN) predicts n-body and interaction energies with an accuracy approaching coupled cluster theory. The performance of DC-SCAN is size-consistent, maintaining an accurate description of molecular interactions well beyond the first solvation shell. Molecular dynamics simulations at ambient conditions with many-body MB-SCAN(DC) potentials, derived from the many-body expansion, predict the solvation structure of Na+ and Cl− in quantitative agreement with reference data, while simultaneously reproducing the structure of liquid water. Beyond rationalizing the accuracy of density-corrected models of ion hydration, our findings suggest that our unified density-corrected MB formalism holds great promise for efficient DFT-based simulations of condensed-phase systems with chemical accuracy. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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